Lubricating oil compositions



United States Patent 3,124,532 LUBRHCATENG 01L COMPOSITIONS G orge W. Ayers, Chicago, 111., assignor to The Pure 0i! Company, Chicago, Ill., a corporation of Ohio No Drawing. Filed Dec. 28, 1959, Ser. No. 862,0?4 12 Claims. (Cl. 252-45) This invention relates to a new composition of matter comprising derivatives of aromatic compounds, particularly aromatic compounds derived from sources rich in complex, polynuclear, high-molecular-weight aromatic compounds, e.g., aromatic compounds contained in solvent extracts obtained in the solvent refining of mineral lubricating oils and fractions of mineral lubricating oils. More particularly, this invention relates to such derivatives as the halomethylated, hydroxymethylated, aminomethylated, cyanomethylated, oarboxymethylated, carbalkoxymethylated, mercaptomethylated and aldelhydomethylated products and di-arylmethyl ethers, thioethers, and disulfides derived from the aromatic and/or heterocyclic compounds of aromatic character obtained from petroleum sources, characterized by their complexity, high molecular weight, polynuclear configuration and cyclic structure.

This invention is based on the discovery that complex, high-molecular-Weight aromatic compounds, particularly aromatic compounds as above-defined derived from petroleum sources, can be successfully halomethylated using the steps that are applied to simple aromatic compounds, such as benzene and napththalene, and that the resulting halomethylated product is not only a useful compound in itself, exhibiting extreme-pressure properties in lubricating oil compositions to an unexpected degree, but can be further subjected to a variety of reactions of halo-compounds to form the aforementioned derivatives. Another feature of the invention, which will be used to demonstrate the formation of a disulfide derivative to confirm the discovery that the halomethylated products form the basis of many types of derivatives, is

that the disulfide derivative is also an extreme-pressure 'agent.

the utilization of complex aromatic compounds present in the lubricating oil portion of petroleum.

An object of this invention is to provide a composition of matter comprising derivatives prepared from halomethylated complex aromatic compounds.

Another object of this invention is to provide a composition of matter comprising derivatives of complex aromatic compounds derived from solvent extracts obtained in the solvent refining of mineral lubricating oils or fractions thereof.

Another object of this invention is to provide a composition of matter comprising halomethylated complex aromatic compounds derived from solvent extracts ob- 3,124,532 Patented Mar. 10, 1964 tained in the solvent refining of mineral lubricating oils and fractions thereof.

A further object of this invention is to provide a composition of matter comprising the disulfide derivative of methylated complex aromatic compounds.

Another object of this invention is. to provide a composition of matter comprising the disulfide derivative of methylated complex aromatic compounds derived from solvent extracts obtained in the solvent refining of mineral lubricating oils or fractions thereof.

Still another object of this invention is to provide such derivatives as hydroxymethylated, aminomethylated, cyanomethylated, carboxymethylated, carbalkoxymethyl ated, mercaptomethylated and aldehydomethylated products and diarylmethyl ethers, thioethers and disulfides derived from complex aromatic compounds obtained from petroleum sources.

Still a further object of this invention is to provide mineral lubricating oil compositions containing amounts of halomethylated complex aromatic compounds derived from solvent extracts sufficient to enhance the lubricating and/ or extreme-pressure properties thereof.

Still a further object of this invention is to provide mineral lubricating oil compositions containing amounts of disulfide derivatives of methylated complex aromatic compounds derived from solvent extracts sufiicient to enhance the lubricating and/ or extreme-pressure properties thereof.

These and further objects of the invention will be described or become apparent as the specification proceeds.

In describing this invention, the term halomethylation is used to mean the replacement of one or more nuclear hydrogen atoms on the complex aromatic compound by a chloromethyl, iodomethyl or bromomethyl group. However, the term halogenated as used herein is intended to include all of the halogen derivatives, that is, chloro, bromo, iodo, and fluoro compounds. Furthermore, the term complex aromatic compound is intended to mean those complex, high-molecular weight, aromatic polynuclear and heterocyclic compounds, including those having sulfur and/or nitrogen in one or more rings exhibiting aromatic character, characterized by being present in small or large proportions in mineral lubricating oils or fractions thereof.

Halomethylation was first performed by Grassi and Maselli in 1898 (Gazz. chim. ital., 28, II, 477) in the synthesis of benzyl chloride by the reaction of benzene, hydrogen chloride, paraformaldehyde and zinc chloride. There are numerous limitations to the reaction. Terphenyl, for example, resists chloromethylation altogether. Monoalkylbenzene derivatives yield parachloromethyl compounds and lesser amounts of ortho isomers. The presence of a halogen atom on the ring causes the reaction to be more difficult to effect, and low yields result from the chloromethylation of bromobenzene, chlorotoluenes, etc. Nitro groups generally inhibit the reaction. Ketones are usually unreactive but acetomesitylene, acetoisodurene, and 2,4,6-triethylacetophenone do react. Phenols react so readily that they tend to form polymers. The formation of the diarylmethane derivative as a sidereaction product is troublesome in many instances. Accordingly, considering the complex nature of the aromatic compounds with which this invention is concerned,

it is unusual to find that these compounds can be so successfully halomethylated.

The haloethylation reaction as applied herein utilizes the known techniques and modifications that have been in use for some time. Any methanal compound may be used which produces formaldehyde. Formalin may be used in some cases, or the formaldehyde may be generated in the reaction mixture by deploymerization of paraformaldehyde (trioxymethylene). In the literature, the terms paraformaldehyde and trioxymethylene are used to refer to polyoxyrnethylenes. The trimer (CH Q) melting at 62-63" C. is called alpha-trioxymethylene, and is anhydrous, whereas paraformaldehyde generally contains from 2 to 5% of water. The reaction may be carried out using the classic method, i.e., formaldehyde and hydrochloric acid, or diethylformal or dimethylformal and hydrochloric acid may be used. Hydrochloric acid, hydrobromic acid, or hydroiodic acid may be used. When halomethyl ethers are used, such as chloromethyl ether, the haloacid may be omitted.

The use of a catalyst for the halomethylation reaction is optional. Zinc chloride, stannic chloride, aluminum chloride, sulfuric acid and acetic acid may be used as catalysts. A catalyst comprising a small amount of aluminum chloride mixed with fused zinc chloride may be used. A preferred method comprises chloromethylation by means of a mixture of formalin or paraformaldehyde and hydrochloric acid in the presence of zinc chloride. The reaction is carried out by heating the mixture of formaldehyde-producing agent, complex aromatic hydrocarbon and haloacid with or without a catalyst to a temperature of about 50 to 100 C. The haloacid may be introduced in gaseous form by rapidly passing a stream thereof through the reaction mixture. This is continued until no more haloacid is absorbed.

At the completion of the reaction, which takes about 30 minutes to 4 hours, the organic layer is separated, washed with Water, and then washed with a dilute sodium bicarbonate solution. This operation removes any occluded catalyst and prevents resinification of the prod- -uct.

A preferred method of preparing the halomethylated product of this invention comprises the use of formaldehyde or paraformaldehyde with a phosphorus oxyhalide as described in copending application Serial Number 855,257, filed November 25, 1959, by George W. Ayers and William C. Allinder, now Patent No. 3,076,039. This method will be used in the examples herein.

Using RH to represent a carbocyclic structure, or a heterocyclic structure with up to three atoms of sulfur or nitrogen in the ring or rings, such as the cyclic structures in polynucle a r aromatics, heterocyclics with aromatic properties, condensed alicyclic-aromatics, condensed heterocyclic-aromatics, and polyheterocyclics with aromatic properties, H to represent a replaceable nuclear hydrogen, and a to represent an integer with a value depending upon the specific cyclic structure, or structures, the following reactions and products are illustrative of the invention:

(7) R (CI-I CN 2aH O (plus acid or base as catalyst): R(-CH COOH) ]-aNH catalyst) =R(CH CH NH In Equations 1 to 6 chlorine may be bromine or iodine instead.

The complex aromatic compounds, RH in the equations and as heretofore referred to, used as the starting material for the derivatives of this invention are found in the mineral lubricating oil portion of petroleum oil. A convenient and inexpensive source of high concentrations of these complex aromatic compounds comprises solvent extracts obtained in the manufacture and refining of neutral oils and bright stocks during treatment with a selective solvent designed to extract the predominantly aromatic materials from the paraifinc materials. Solvent extracts resulting from the treatment of mineral lubricating oils for the purpose of separating non-aromatic hydrocarbons (the raffinate and finished oil) from the aromatic hydrocarbons (the extract and waste product) may be used and are preferred as starting materials.

Since the general process of refining mineral lubricating oils in which solvent extracts are obtained is well 'known, it is only necessary for present purposes to describe a typical procedure for obtaining same and give some examples by way of illustration.

In a typical operation, desalted crude oil is first charged to a distillation unit where straight-run gasoline, two grades of naphtha, kerosine, and virgin distillate are taken off, leaving a reduced crude residue. The reduced crude is continuously charged to a vacuum-distillation unit where three lubricating oil distillates are taken off as side streams, a light distillate is taken off as overhead, and a residuum is withdrawn from the bottom of the tower. The residuum is charged to a propane-deasphalting unit wherein propane dissolves the desirable lubricating oil constituents and leaves the asphaltic materials. A typical vacuum-residuum charge to the propane-deasphalting unit may have an API gravity of 129, viscosity SUS at 210 F. of 1249, flash 585 F, fire 650 F., C.R. of 13.9 weight percent, and may be black in color. The deasphalted oil may have an API gravity of 21.5 to 21.8",

viscosity SUS at 210 F. of 165475, NPA color 67,

flash 575 F., fire 640 F., and C.R. of 1.7-2.0 wt. percent. The deasphalted oil and various lubricating oil distillates from the reduced crude are subjected to solvent extraction for the separation of non-aromatic from aromatic constituents prior to use. The refined oil or raf finate from the extraction processes is used per se; extract, predominating in complex aromatic constituents, is distinctively useful in accordance with this invention.

For example, a crude oil from an East Texas field with an API gravity of 33.1 was topped to remove such light fractions as gasoline, naphtha, kerosine, and a light Inbricating distillate. A second lubricating-oil distillate cut was then obtained which had a viscosity of 240 SUS at F, 1.0 weight percent sulfur, and an API gravity of 24.5". This oil was treated with phenol to produce a raffinate from which a high-quality lubricating oil could be prepared. The oil extracted by phenol treatment, after removal of phenol, is ready for use as the starting material in accordance with this invention.

Solvents other than phenol may be used to obtain the extraction product used in accordance with this invention, for example, liquid sulfur dioxide, nitrobenzene, Chlorex, chlorophenol, cresylic acid, furfural, or the Duo- Sol solution (comprising liquid propane and cresol) may be used. When using phenol, it is possible to vary the characteristics of the extract and railinate products considerably by adjustment of the amount of water present. A raffinate of relatively low viscosity index can be obtained by using anhydrous phenol. Following are the physical characteristics of typical extract products, from lubricating oil stocks derived from various crude oils and in accordance with this invention.

TABLE I Sources and Physical Characteristics of Solvent Extracts Tests on the Solvent Extract Ext. No. Crude Source Solvent Aver- API Vis./ V.I. Pour F. F. Percent Percent age Mo- Grav. 210 F Flash Fire 0. Sulfur lecular Weight The solvent extracts from lubricating oils used as starting materials for this invention have the following general properties and characteristics:

TABLE II Characteristic: Range of value Gravity, API 7.3-18.3. Gravity, Sp., 60/60" F 09446-10195. Viscosity SUS 210 F 40-1500. Viscosity index Minus 153 to plus 39.

Pour point, F -115. Color, NPA +2-5D. Molecular weight, average Above 300. Sulfur, percent wt Above 0.6. Nitrogen, percent wt Below 1. Aromatic compounds, vol. percent (including heterocyclics) 7598. Av. No. of aromatic rings/mean arom. mol 1.7-3.5.

The specific gravities of the extracts in general increase with increase in the viscosity of the rairinate at a constant viscosity index. Stated otherwise, the specific gravities of these extracts increase with decrease in viscosity index of the rafiinate at a constant viscosity. For the production of 100:5 VI neutral oils, the viscosities of the extracts increase with increase in stated viscosities of the neutral oils (raffinates). The pour points of extracts are 'high and are affected by changes in the depth of extraction. The sulfur contents are also affected by the depth of extraction. The solvent extracts are characterized by containing aromatic and heterocyclic compounds in the range of 75-98 vol. percent, the remainder being principally saturates, or material behaving as saturates, together with a minor proportion of up to 7% of organic acids. The organic acids present are not susceptible to extraction by the use of aqueous strong caustic because of the solubility of the sodium salts of the acids in the oil. Little or no asphaltic material is present in solvent extracts and they contain no materials volatile at room temperature.

The data shown in Tables I and II are merely illustrative and the invention is not to be limited thereby.

It is apparent that the characteristics of the final halomethylated product and the various derivatives prepared therefrom will vary depending on the concentration and types of complex aromatic starting materials employed. In such complicated mixtures as solvent extracts from lubricating oil fractions, the content of reactable materials may vary from about 30% to by weight of the aromatic and heterocyclic material present. Smaller concentrations of reactable complex aromatic compounds may be used than are found in solvent extracts. However, it has been found that solvent extracts contain source materials which are peculiarly adapted to this reaction, thus providing a new use for this otherwise waste product. It is only necessary to free the solvent extract of any selective solvent, and the solvent extract then may be used directly or it may be diluted with naphtha or mineral oil in the halomethylation reaction. In the preparation of the various derivatives from the halomethylated solvent extract, it may be necessary to also apply the dilution technique. In any event a minimum of about 10% of reactable materials should be used in all steps of the preparation in order to make the process economical as a unit process for petro-chemical manufacture.

As described in said copending application using phos phorus oxyhalide, e.g., phosphorus oxychloride, for the reaction, any formaldehyde-producing agent may be used. Any formaldehyde polymer yielding substantially anhydrous formaldehyde under the conditions of the process may be employed in this process. Ordinarily, the stoichiometric amount (based on the chlorine content of the product), or slightly more than the stoichiometric amount, of formaldehyde (or formaldehyde polymer) is used in our process. Aqueous solutions of formaldehyde, such as formalin, cannot be used directly in the present process. If desired, the formaldehyde (or paraformaldehyde) may be added to the phosphorus oxychloride, and the mixture used in chloromethylation of the aromatic compound or mixture of aromatic substances.

The preferred reaction temperature is approximately 4060 C., although the process may be carried out at temperatures from 20 to C., or even higher. The use of higher temperatures may favor condensation of the aromatic material to higher-molecular-weight substances at the expense of chloromethylated products.

For this chloromethylation process, sulficient phosphorus oxychloride is used to furnish the halogen in the chloromethylated product. Stoichiometrically, one mol of phosphorus oxychloride is required for each three mols of formaldehyde, which then react with the aromatic to form the chloromethylated product. In practice, somewhat more phosphorus oxychloride may be advantageous, but too great an excess of phosphorus oxychloride may cause an excessive amount of condensation, producing a high-molecular-weight, chloromethylated product.

Phosphorus trichloride and phosphorus pentachloride are not effective replacements for phosphorus oxychloride in this process. However, phosphorus oxybromide or phosphorus oxyiodide may be used to prepare bromomethylated or iodomethylated products instead of chloromethylated products. 7

A solvent composed of one or more parafinic or cycloparafiinic hydrocarbons not susceptible to chloromethylation may be used to dissolve the aromatic reactant prior to chloromethylation by this process. The solvent used must boil below the initial boiling point of the aromatic reactant so that it can be removed from the chloromethylated product by distillation.

This process may be carried out either batchwise or continuously. Whatever process is used, provision must be made for controlling temperature since the reaction is exothermic. It is carried out best at approximately 4060 C. Under such conditions, the reactants should be maintained in contact with one another until the exo thermic reaction has subsided. This period may be as long as three hours or even longer. Further heating for several hours is conducive to maximum yields.

In order to demonstrate the invention the following examples are given.

EXAMPLE I A three-neck, 500-cc. glass flask was fitted with a mechanical stirrer, thermometer, and reflux condenser, and was immersed in a water bath containing water at room temperature. After 165 gms. (0.49 mol) of solvent extract (No. 19 of Table I) and 18.2 gms. (0.63 mol) of paraformaldehyde had been added to the flask and stirred mechanically, 30.7 gms. (0.2 mol) of phosphorus oxychloride were added in small portions during 10 to minutes, while the stirring was continued. After addition of the phosphorus oxychloride was completed, the water in the bath was heated slowly. When the temperature of the reaction mixture reached approximately 40 C., rapid reaction took place with foaming, and heating of the water bath was discontinued. Reaction proceeded during the next three hours, at the end of which time the temperature had reached approximately 77 C. Stirring of the reaction mixture was continued about three hours longer, heating the water bath whenever necessary to maintain the temperature of the mixture in the flask between 53 C. and 79 C. The reaction mixture was diluted with approximately 200 ml. of benzene, filtered to remove a small amount of tarry material, and then washed with -EXA1\IPLE IV A preparation similar to that of Example I was carried out using phosphorus trichloride instead of phosphorus oxychloride. The product contained only 0.25% chlorine by analysis, showing that phosphorus trichloride was relatively ineffective in conjunction with paraformaldehyde as a chloromethylating agent.

EXAIMPLE V A preparation was carried out as in Example I, but with phosphorus pentachloride instead of phosphorus oxychloride. The product contained only 1.1% chlorine by analysis, and the chlorine was practically all unreactive to silver nitrate. This indicated that some nuclear chlorination rather than chloromethylation had taken place during the run.

EXAMPLE VI Extract No. 19 of Table I was chloromethylated in six batches by adding phosphorus oxychloride dropwise to well-stirred separate mixtures of the extract with paraformaldehyde. The reaction began at a temperature of about C. External cooling was applied intermittently in order to control the foaming which resulted. The reaction product was diluted with 1 to 3 volumes of benzene, filtered to remove tarry substances, and the filtrate was washed with water until free of mineral acids. The benzene was removed from the chloromethylated product by distillation. Varying amounts of extract, paraformaldehyde, and phosphorus oxychloride were used in some of these runs. The sixth run was carried out in the absence of paraformaldehyde to show that phosphorus oxychloride by itself under these conditions causes only negligible chlorination of the product. In Experiment No. 4, dry hydrogen chloride gas was passed through the reaction mixture during the entire reaction period in order to determine whether this would increase the exwater until the water washings were free of chloride ion tent of chloromethylation of the aromatic extract. The and no longer gave a test for free mineral acid with results are shown inTable III.

TABLE III Chloromethylation 0 Extract N0. 19

Reactants Reaction Product Maxi- Exp. mum Re- Yield N0. Extract Para- Phosaction (g.) Percent No. 19 formalphorus Temp. Percent Percent Phos- (g.) dehyde Oxychlo- (C.) Chlorine Sulfur phorus (e) nde (a) 1 82.5 9.4 15.3 105 2 165.0 18.8 30.7 104 366 4 5 22 Nil. 3 165.0 18.8 30.7 83 4 165.0 18.8 30.7 82 4 3 Nil. 5 165.0 36.8 61.3 61 132 7 0 Nil. 6 165.0 30.7 97 0 2 Nil.

methyl orange indicator. The benzene was removed by distilluation, leaving a greenish-black chloromethylated product containing 4.45% chlorine, by analysis. This chlorine was reactive toward silver nitrate and represented approximately 50% chloromethylation of the extract.

EXAMPLE II Solvent Extract No. 19 was chloromethylated as in Example I except that a stream of hydrogen chloride was constantly passed through the reaction mixture during the preparation. The product contained 4.3% chlorine by case the chloromethylated solvent extract was dissolved in xylene before contacting with the sodium disulfide solution. In each case, the product was washed successively with sodium sulfide solution, sodium hydroxide solution and with water in order to remove traces of sulfur or other unwanted substances from the product. Any solvent present in the product was removed by distillation. The sulfur and chlorine contents of the final products are shown in Table IV. In each case, only a portion of the chlorine contained in the chloromethylated extract was replaced by disulfide sulfur.

Several lubricant blends containing various amounts of a phosphosulfurized sperm oil base, chloromethylated extract, the disulfide product of Example VII, dibenzyl disulfide, a VI improver and mineral oil are compared with a known extreme-pressure additive of the chlorinatedwax type in Table V.

TABLE IV Disulfide Products From Chloromethylated Solvent Extract Reactants Disulfide Product 1 Ohloro- Contact Exp. methylated Sodium Time at No. Extract Disulfide Xylene, 7480 0., Percent Percent (Combined Solution, g. hrs. Sulfur Chlorine Expts. 1-3 g. of Table I), gms.

1 The chloromethylated solvent extract from which the disulfide products were prepared contained 2.2% sulfur and 4.5% chlorine.

2 Solvent extract contains sulfur compounds which are not disulfides. The values given for sulfur content include in each case the sulfur due to carryover of the sulfur compounds in the original extract.

3 Solution of 5.5 g. sodium sulfide nonahydrate and 0.7 g. sulfur in 14 g. water.

4 Solution of 11.0 g. sodium sulfide nonahydrate and 1.4 g. sulfur in 28 g. water.

TABLE V El. Properties of Lubricant Blends Containing Chloromethylated Extract Lubricant Blend A B O D E F Composition of Lubricant Blend:

Phosphosulfurized The invention has been illustrated by a number of nonlimiting examples using solvent extracts as the source of the complex aromatic compounds. The process also may be applied to complex aromatic compounds in a mineral oil prior to solvent extraction in order to form the derivatives in situ. Furthermore, since the amount of the extracted hydrocarbons may vary with the type of solvent used, the type of mineral oil being solvent treated, i.e., whether it is from a paraffinic, naphthenic or mixed base crude, some adjustment in composition by blending extracts from different sources may be made in order to arrive at complex aromatic starting materials exhibiting the unique properties as derivatives in accordance with the invention. Also, the more reactive complex aromatics in the solvent extracts may be isolated or concentrated and used as the starting material. As a guide in selecting the starting materials and further characterizing the extracts used herein or contemplated by this invention the following is given:

The average molecular weight of solvent extracts obtained in the preparation of 200 vis. neutral oils is about 340. These extracts contain about 75% to 87 by vol. percent of complex aromatic hydrocarbons and heterocyclics of aromatic character having an average of about 2.7 carbon rings per aromatic molecule. The polynuclear aromatics from petroleum sources contain a predominance of aromatic substances having two to three carbon rings per aromatic molecule and have an average molecular weight of above 300. The extracts obtained during the manufacture of 150-160 vis. bright stocks contain from to 98 vol. percent of complex aromatics and heterocyclics having an average of about 3.3 aromatic rings per mean aromatic molecule. When a typical solvent extract was subjected to carbon-type analysis using the method of Kurtz, King, Stout, Partikan and Skrabek (Anal. Chem, 28, 1928 (1956)), the results were: C 39%, C 30%, and C 31%. In this analysis, the C include only the carbon atoms present as parafiins and as side chains on the aromatic and naphthene rings. This same extract, No. 19 in Table I, had an average molecular weight of 340, contained 84% aromatics (and heterocyclics of aromatic type), as determined by the silica gel procedure, and showed 12.5% saturated hydrocarbons, etc., 86.4% carbon and 10.7% hydrogen.

The complexity of the types of compounds present, as based on these analyses, is illustrated by the following table:

TABLE VI Estimated Chemical Composition of Solvent Extracts Nos. 19 and 21 of Table I Approx. percent Type of compoundin the extract Saturated hydrocarbons 12.5 Mononuclear aromatics: Substituted benzenes- 25.0 Dinuclear aromatics: Substituted napthalenes 3-0.0 Trinuclear aromatics:

Substituted phenanthrenes 10.0

Substituted anthracenes 5.0 Tetranuclear aromatics:

Substituted chrysenes 0.5

Substituted benzphenanthrenes 0.2

Substituted pyrenes 0.2 Pentanuclear aromatics: Perylene 0.01 Sulfur compounds, oxygen compounds, etc. 16 .5

1 Mainly heterocyclic compounds.

EXAMPLE VIII A portion of the chloromethylated product from Example I, dissolved in twice its volume of toluene is heated under reflux conditions With an excess of 20% aqueous sodium hydroxide solution for one hour to replace the chlorine by hydroxyl. The toluene layer is separated, and washed four times with Water; then the toluene is removed by distillation. The residue from the distillation is a hydroxymethylated product.

EXAMPLE IX A portion of the chloromethylated product from Exampic I, dissolved in an equal volume of toluene, is contacted with liquid ammonia for four hours at approximately 0 C. The excess ammonia is then volatilized gradually by allowing the mixture to warm to room temperature. The toluene solution is then heated with an excess of 5% sodium hydroxide solution until no more ammonia is evolved, after which it is separated and Washed four times with water. After the toluene is removed by distillation, the material remaining undistilled is a mixture of primary, secondary and tertiary amines, together with a small amount of quaternary substituted ammonium compounds.

EXAMPLE X A 25 g. portion of the chloromethylated product from Example 1 dissolved in 100 cc. of toluene, is added dropwise during the course of one hour to a mechanicallystirred solution of 25 g. sodium cyanide in 150 cc. of water, the reaction mixture being held at approximately 100 C. during the course of the experiment. The toluene layer is then separated, washed twice with water, and the toluene removed from a portion of the material by distillation. The residue from the distillation is a cyanomethylated product containing organic nitriles.

The remainder of the toluene solution is then heated under reflux conditions with 75 cc. of 5% aqueous sodium hydroxide solution for four hours, cooled to ambient temperature, acidified carefully with 100 cc. of 5% aqueous sulfuric acid solution, and finally refluxed for five minutes. The toluene layer is removed, washed four times with water, and the toluene removed by distillation. The distillation residue is a carboxymethylated product containing organic acids.

From this description it is apparent that this invention relates to compositions of matter including derivatives of the general formula wherein R is a complex polynuclear hydrocarbon radical obtained from the lubricating oil portion of petroleum, particularly solvent extracts or the reactable portion of solvent extracts; A is a substituent group such as halogen, acetamido, acetonyl, acetoxy, alkoxy, amino, anilino, arylmethyl disulfido, arylmethyl sulfido, benzamido, benzidino, benzoxy, butoxy, caproxy, capryloxy, carbamyl, cinnamoxy, carboxyl, crotonoxy, cyano, ethoxy, formamido, formoxy, furoxy, heterocycylmethyl disulfido, heterocyclylmethyl sulfido, hydroxyl, isoamoxy, isobutoxy, isopropoxy, isothiocyano, mercapto, methoxy, rnorpholinyl, naphthoxy, palmitoxy, phenacyl, phenoxy, piperidyl, propoxy, pyridyl, pyrryl, quinol-inyl salicyloxy, stearoxy, succinamido, succinimido, tetrahydrofuroxy, thiocyano and valeroxy, or A may be a hydrocarbon group, e.g., an alkyl group, containing from 1 to 24 carbon atoms, an aryl group containing from 6 to 15 carbon atoms, an alkaryl group containing from 7 to 39 carbon atoms, or an aralkyl group containing from 7 to 39 carbon atoms or more; and x is any integer from 1 to 3. The invention also relates to disulfide and diselenide compounds of the formula where S may be sulfur or selenium; alcohols of the formula R(CH OH) ethers of the formula RCH OOH R quaternary ammonium compounds of the formula (RCH NX where X is a halogen; acids of the formula R(CI-I COO1H) and amines of the formula wherein in each instance R has the foregoing definition. As a subgeneric definition of the invention, A may be hydrogen, an alkyl, aryl or aralkyl oxido radical, a halogen, or an aldehyde group. For example, compounds of the formulas R-C H RCH -OCH R(CH X) wherein X is Cl, Br, I or F and x is l-3, and

are included wherein R has the foregoing definition.

Having thus defined the invention and given non-limiting examples the only limitations attaching thereto appear in the appended claims.

What is claimed is:

1. A composition of matter of the formula wherein R is a complex, polynuclear sulfur and nitrogencontaining heterocyclic nuclei derived from solvent extracts obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and is characterized by having an average molecular weight of above about 300, a sulfur content of above about 0.6 wt. percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

3. A composition of matter of the formula R(CH OH) x wherein x is an integer from 1 to 3 and R is a complex, pol-ynuclear sulfur and nitrogen-containing heterocyclic nuclei derived from solvent extracts obtained in the solvent refining of mineral lubricating oils using -a solvent selective for aromatic compounds and is characterized by having an average molecular weight of above about 300, a sulfur content of above about 0.6 wt. percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

4. A composition of matter of the formula (RCH NH X wherein x is a halogen, b is an integer from 1 to 4 and c has a value of 0 to 3, the sum of a and b being equal to 4 and R is a complex, polynuclear sulfur and nitrogen-containing heterocyclic nuclei derived from solvent extracts obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and is characterized by having an average molecular weight of above about 300, a sulfur content of above about 0.6 wt. percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

5. A composition of matter of the formula wherein x is an integer from 1 to 3 and R is a complex, polynuclear sulfur and nitrogen-containing heterocyclic nuclei derived from solvent extracts obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and is characterized by having an average molecular weight of above about 300, a sulfur content of above about 0.6 wt. percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

6. A composition of matter of the formula R(CH COOH) wherein x is an integer from 1 to 3 and R is a complex, polynuclear sulfur and nitrogen-containing heterocyclic nuclei derived from solvent extracts obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and is characterized by having an average molecular weight of above about 300, a sulfur content of above about 0.6 wt. percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

7. An extreme pressure lubricant consisting essentially of a major portion of a mineral lubricating oil and about 2.5 to 5.0 wt. percent of a composition of matter of the formula wherein X is a halogen, x is an integer from 1 to 3 and R is a complex, polynuclear sulfur and nitrogen-containing heterocyclic nuclei derived from solvent extracts obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and is characterized by having an average molecular weight of above about 300, a sulfur content of above about 0.6 wt. percent and an average number of about 1.7 to 315 aromatic rings per mean aromatic molecule.

8. A composition in accordance with claim 7 in which R is further characterized by having the following characteristics Characteristic Range of value Gravity, API 7.318.3. Gravity, Sp., 60/ 60 F 09446-10195. Viscosity SUS 210 F. 40-1500. Viscosity index Minus 153 to plus 39. Pour point, F. 20-115. Color, NPA +2-5D. Nitrogen, percent wt. Below 1. Aromatic compounds, percent including heterocyclics 75-98.

9. An extreme pressure lubricant consisting essentially of a major portion of a mineral lubricating oil and about 2.5 to 5.0 wt. percent of a composition of matter of the formula wherein R is a complex, polynuclear sulfur and nitrogencontaining heterocyclic nuclei derived from solvent extracts obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and is characterized by having an average molecular 14 Weight of above about 300, a sulfur content of above about 0.6 wt. percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

10. A composition in accordance with claim 9 in which R is further characterized by having the following characteristics Characteristic- Range of value Gravity, API 73-183. Gravity, Sp., 60 F 09446-10195. Viscosity SUS 210 F. 40-1500. Viscosity index Minus 153 to plus 39. Pour point, F. 2-0-115. Color, NPA +2-5D. Nitrogen, percent wt. Below 1. Aromatic compounds, percent including heterocyclics -98.

11. An extreme pressure lubricating composition consisting essentially of a major portion of a mineral lubricating oil, about 10% by weight of phosphosulfurized sperm oil and between about 1.0 to 5.0% by weight of ohloromethyl ated solvent extract, said solvent extract being obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and characterized by having an average molecular weight above about 300, sulfur content above about 0.6- weight percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

12. An extreme pressure lubricating composition consisting essentially of a major portion of a mineral lubri eating oil and about 10% by weight of phosphosulfurized sperm oil and about 2.5 to 5.0% by weight of the disulfide product of solvent extract, said solvent extract being obtained in the solvent refining of mineral lubricating oils using a solvent selective for aromatic compounds and characterized by having an average molecular weight above about 300, sulfur content above about 0.6 Weight percent and an average number of about 1.7 to 3.5 aromatic rings per mean aromatic molecule.

References Cited in the file of this patent UNITED STATES PATENTS 1,425,393 Laska Aug. 8, 1922 2,185,008 Wojcik Dec. 26, 1939 2,186,271 Pevere Jan. 9, 1940 2,250,384 Lincoln et a1. July 22, 1941 OTHER REFERENCES Adams et al.: Organic Reactions, pub. by John Wiley & Sons, New York, N.Y., vol. I, 1954, pages 6 5-90. 

7. AN EXTREME PRESSURE LUBRICANT CONSISTING ESSENTIALLY OF A MAJOR PORTION OF A MINERAL LUBRICATING OIL AND ABOUT 2.5 TO 5.0 WT. PERCENT OF A COMPOSITION OF MATTER OF THE FORMULA
 9. AN EXTREME PRESSURE LUBRICANT CONSISTING ESSENTIALLY OF A MAJOR PORTION OF A MINERAL LUBRICATING OIL AND ABOUT 2.5 TO 5.0 WT. PERCENT OF A COMPOSITION OF MATTER OF THE FORMULA 